Organometal catalyst compositions

ABSTRACT

This invention provides oxide matrix compositions that can be utilized in catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. The oxide matrix composition comprises residual mineral components and an oxide precursor. The catalyst composition comprises contacting an organometal compound, an organoaluminum compound, and an oxide matrix composition. Processes for producing the oxide matrix composition and the catalyst composition are also provided.

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/174,045 filed Dec. 30, 1999.

FIELD OF THE INVENTION

[0002] This invention is related to the field of organometal catalystcompositions.

BACKGROUND OF THE INVENTION

[0003] The production of polymers is a multi-billion dollar business.This business produces billions of pounds of polymers each year.Millions of dollars have been spent on developing technologies that canadd value to this business.

[0004] One of these technologies is called metallocene catalysttechnology. Metallocene catalysts have been known since about 1958.However, their low productivity did not allow them to be commercialized.About 1974, it was discovered that contacting one part water with onepart trimethylaluminum to form methyl aluminoxane, and then contactingsuch methyl aluminoxane with a metallocene compound, formed ametallocene catalyst that had greater activity. However, it was soonrealized that large amounts of expensive methyl aluminoxane were neededto form an active metallocene catalyst. This has been a significantimpediment to the commercialization of metallocene catalysts.

[0005] Fluoro-organo borate compounds have been use in place of largeamounts of methyl aluminoxane. However, this is not satisfactory, sincesuch borate compounds are very sensitive to poisons and decomposition,and can also be very expensive.

[0006] Clays having a lamellar structure have also been used to activatemetallocenes, however, activity has not been high in the absence ofcation exchanging or pillaring agents. Pillaring occurs when cationsbetween the layers are replaced by other cations, usually more bulky andsometimes organic cations, that are called pillars due to their role ofpropping open the microscopic sheets and thus slightly expanding thelayered structure of the clay to slightly increase its porosity. Clayalso tends to be fine and dusty making it difficult to handlecommercially in polymerization processes.

[0007] It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniform particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts; however, these catalysts have notbeen entirely satisfactory.

[0008] An object of this invention is to provide a process for producinga new type of high porosity, amorphous, oxide matrix compositioncomprising residual elements of a layered mineral and an oxide compoundprecursor. This oxide matrix composition can be utilized as an activatorfor metallocenes.

[0009] Another object of this invention is to provide the novel oxidematrix composition.

[0010] Another object of this invention is to provide a process thatproduces a catalyst composition that can be used to polymerize at leastone monomer to produce a polymer.

[0011] Another object of this invention is to provide the catalystcomposition.

[0012] Yet another object of this invention is to provide a processcomprising contacting at least one monomer and the catalyst compositionunder polymerization conditions to produce the polymer.

[0013] Still another object of this invention is to provide an articlethat comprises the polymer produced with the catalyst composition ofthis invention.

SUMMARY OF THE INVENTION

[0014] In accordance with an embodiment of this invention, a process isprovided to produce an oxide matrix composition. The process comprises(or optionally, “consists essentially of,” or “consists of”):

[0015] 1) substantially decomposing or exfoliating at least one layeredmineral to produce residual mineral components;

[0016] wherein the layered mineral is a clay, clay mineral, or other ionexchanging compound having a layered crystal structure;

[0017] 2) contacting the residual mineral components and at least oneoxide compound precursor to produce a first mixture;

[0018] wherein the oxide compound precursor is selected from the groupconsisting of a silica source, alumina source, aluminosilicate source,aluminophosphate source, or combinations thereof.

[0019] 3) subjecting the first mixture to such conditions to form a gelor precipitate; and

[0020] 4) calcining the gel or precipitate at a temperature in the rangeof about 150° C. to about 800° C. to produce the oxide matrixcomposition.

[0021] In accordance with another embodiment of this invention, theoxide matrix composition is provided. The novel matrix oxide compositionconstitutes a previously unknown type of oxide matrix compositioncomprising residual mineral components and an oxide precursor compound.The oxide matrix composition has a high porosity and an amorphousstructure, which is unlike that of previously known oxides and minerals.

[0022] In accordance with another embodiment of this invention, aprocess to produce a catalyst composition is provided. The processcomprises contacting an organometal compound, an organoaluminumcompound, and an oxide matrix composition to produce the catalystcomposition,

[0023] wherein the organometal compound has the following generalformula:

(X¹)(X²)(X³)(X⁴)M¹

[0024] wherein M¹ is selected from the group consisting of titanium,zirconium, and hafnium;

[0025] wherein (X¹) is independently selected from the group consistingof cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;

[0026] wherein substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls of (X¹) are selectedfrom the group consisting of aliphatic groups, cyclic groups,combinations of aliphatic and cyclic groups, silyl groups, alkyl halidegroups, halides, organometallic groups, phosphorus groups, nitrogengroups, silicon, phosphorus, boron, germanium, and hydrogen;

[0027] wherein at least one substituent on (X¹) can be a bridging groupwhich connects (X¹) and (X²);

[0028] wherein (X³) and (X⁴) are independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

[0029] wherein (X²) is selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, substituted fluorenyls, halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups;

[0030] wherein substituents on (X²) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticgroups and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

[0031] wherein at least one substituent on (X²) can be a bridging groupwhich connects (X¹) and (X²);

[0032] wherein the organoaluminum compound has the following generalformula:

Al(X⁵)_(n)(X⁶)_(3−n)

[0033] wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbonatoms;

[0034] wherein (X⁶) is a halide, hydride, or alkoxide; and

[0035] wherein “n” is a number from 1 to 3 inclusive.

[0036] In accordance with still another embodiment of this invention, aprocess is provided comprising contacting at least one monomer and thecatalyst composition under polymerization conditions to produce apolymer.

[0037] In accordance with yet another embodiment of this invention, anarticle is provided. The article comprises the polymer produced inaccordance with this invention.

[0038] These objects, and other objects, will become more apparent tothose with ordinary skill in the art after reading this disclosure.

BRIEF DESCRIPTION OF THE FIGURE

[0039]FIG. 1 shows the X-ray diffraction pattern of the inventive oxidematrix composition and a bentonite control.

DETAILED DESCRIPTION OF THE INVENTION

[0040] In a first embodiment of this invention, a process is provided toproduce an oxide matrix composition. The process comprises: 1)substantially exfoliating or decomposing at least one layered mineral toproduce residual mineral components; 2) contacting the residual mineralcomponents and at least one oxide precursor compound to produce a firstmixture; 3) subjecting the first mixture to such conditions to form agel or precipitate; and 4) drying and calcining the gel or precipitateat a temperature in the range of about 150° C. to about 800° C. toproduce the oxide matrix composition.

[0041] The layered mineral is selected from the group consisting ofclay, clay minerals, ion exchanging layered compounds, diatomaceousearth, silicates, and zeolites. These layered minerals can be natural orsynthesized products. Clays are composed of fine crystals or particlesof clay minerals with or without other rock or mineral particles. Thesefine crystals or particles of clay minerals have a diameter of about 3.9micrometers or less and are arranged in layers or sheets. Generally,clays contain more than one clay mineral, and the clay minerals differin chemical and physical properties. Clay minerals are usually the mainconstituent in the clay. Clay minerals are hydrous silicates ofaluminum, magnesium, iron, and other less abundant elements. Morespecifically, a clay mineral is an inorganic polymeric compoundcomprising a tetrahedral unit and an octahedral unit. The tetrahedralunit usually comprises a central silica ion that coordinates to oxygenions. The tetrahedral unit can also be aluminum and other ions thatcoordinate to oxygen ions. The octahedral unit comprises a centralaluminum, magnesium, or iron ion that coordinates oxygen or hydroxideions.

[0042] Specific examples of clay, clay minerals, and ion exchanginglayered compounds include, but are not limited to, kaolin, bentonite,kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, talc,a mica group, a montmorillonite group, vermiculite, a chlorite group,palygorskite, kaolinite, nacrite, dickite, halloysite, layeredsilicates, and mixtures thereof.

[0043] Specific examples of layered silicates include, but are notlimited to, lithium silicate, sodium silicate, potassium silicate,magnesium silicate, calcium silicate, barium silicate, aluminumsilicate, titanium silicate, zirconium silicate, an olivaine group suchas olivaine and fayalite, a garnet group such as garnet, a phenacitegroups such as phenacite and willemite, zircon, tricalcium silicate,merrillite, gehlenite, benitoite, beryl, cordierite, a pyroxene groupsuch as enstatite, hypersthene, diopside, spondumene, rhodonite, andwollastonite, an amphibole group such as anthophyllite, tremolite andactinolite, a feldspar group such as orthoclase, albite, barium feldsparand anorthite, a sodalite group such as sodalite and nocerite, analcite,and natrolite.

[0044] The layered mineral is substantially decomposed or exfoliated toits residual mineral components by any means known in the art. Thedecomposing or exfoliating of the layered mineral can be accomplished bycontacting the layered mineral with a digestion agent selected from thegroup consisting of an aqueous solvent or other protic solvent followedby high shear mixing, high energy sonnification, grinding or milling toproduce a colloidal suspension of residual mineral components.Preferably, the layered mineral is decomposed in a dilute aqueous oralcoholic solution by heating the solution in an acidic or basic mediumat a temperature in the range of about 40° C. to about 100° C. for aperiod of about 1 minute to about a day. Typically, the pH of the acidicmedium is less than about 3, and the pH of the basic medium is greaterthan about 10. Preferably, the heating under acidic or basic conditionsis conducted for about 10 minutes to about 8 hours, and most preferably,30 minutes to 6 hours.

[0045] The decomposition is complete when the layered mineral no longerhas its original layered structure. The decomposition of the layeredmineral can be detected by an increase in the viscosity of the colloidalsuspension. If, after the oxide matrix composition is formed, theoriginal sharp X-ray diffraction lines of the layered mineral have beenreplaced by a simple broad amorphous band, indicating loss of theoriginal structure of the layered mineral, then the decompositionprocess was successful.

[0046] After decomposition of the original layered structure, theresidual mineral components then are contacted with an oxide precursorcompound to produce a first mixture. The oxide precursor compound isselected from the group consisting of a silica source, an aluminasource, a phosphate source or combinations thereof. Any source ofungelled silicate solution can be used as an oxide precursor compound,including hydrocarbon or alcohol soluble organic silicates, such as,tetraethylorthosilicate, tetrabutylorthosilicate, or silicontetrachloride, can be used. Ungelled silicate solutions are disclosed inU.S. Pat. Nos. 4,301,034; 4,547,557; and 4,339,559; the entiredisclosures of which are herein incorporated by reference. An inorganicwater soluble silicate, such as, for example, sodium silicate, waterglass, and potassium silicate, can also be utilized as an oxideprecursor compound in this invention. Inorganic water soluble silicatesare disclosed in U.S. Pat. Nos. 3,900,457; 2,825,721; 3,225,023;3,226,205; 3,622,521; and 3,625,864; the entire disclosures of which arehereby incorporated by reference. Aluminum salts, such as, for example,aluminum nitrate, aluminum chloride, aluminum acetate, aluminum sulfate,and mixtures thereof can be used as an alumina source. Organic aluminumcompounds can also be utilized as an alumina source in this invention.Examples of organic aluminum compounds include, but are not limited toaluminum isopropoxide, aluminum acetylacetonate, and mixtures thereof.Organic aluminum compounds are disclosed in U.S. Pat. Nos. 4,364,842;4,444,965; 4,364,855; 4,504,638; 4,364,854; 4,444,964; and 4,444,962;the entire disclosures of which are herein incorporated by reference.Anhydrous aluminum chloride can also be used as an oxide compound ifdissolved in an aprotic solvent. Combinations of aluminum and silicasources also can be used. Other oxide compounds also can be present inthe silica sources, alumina sources, and silica-alumina sources, suchas, titania, zirconia, boria, magnesia, iron oxide, chromium oxide, oraluminophosphates. Preferably, the majority of the oxide precursorcompound comprises silica.

[0047] The first mixture then is subjected to such conditions to form agel or precipitate. Any gellation or precipitation method known in theart can be utilized. Preferably, the first mixture is gelled byadjusting the pH to within a range of about 4 to about 9. This gellationcan be suddenly, as when aluminum hydroxide is precipitated by addingbase to an acidic solution of aluminum ions, or it can take hours, aswhen a silica sol is allowed to set up and gel gradually. Gellation canoccur when the first mixture is acidic or basic. For example, sodiumsilicate can be added to a nitric acid solution containing the residualmineral components. This method is disclosed in U.S. Pat. Nos. 3,887,494and 3,1119,569; the entire disclosures of which are hereby incorporatedby reference. Another method is to add sulfuric acid to a sodiumaluminate solution containing the residual mineral components to producea gel.

[0048] Optionally, the gel is aged for a specified period of time. Agingof the gel is preferred in order to impart strength to the gel. To agethe gel, it is allowed to stand at a temperature in the range of about60 to about 100° C. for about 5 minutes to about 10 hours, preferablyfrom 1 hour to 5 hours. Preferably, the aging step is conducted in thepresence of at least some water at a pH of greater than about 8 and mostpreferably, at a pH greater than about 9. Processes for aging a gel aredisclosed in U.S. Pat. Nos. 4,405,501; 4,436,882; and 4,981,831; theentire disclosures of which are hereby incorporated by reference.

[0049] Optionally, the gel or precipitate is washed with an aqueoussolution. Washing is preferred in order to remove salts formed from thegellation step. Washing can also sometimes be desirable if the gel iswashed in an acidic aqueous solution to remove some cations contained inthe original layered mineral, making it more acidic. After aging, thegel is washed in water sufficiently to remove unwanted ions, such asresidual sodium or sulfate ions. Optionally, the gel then can be washedwith an alcohol or other organic liquid of low surface tension, or itcan be azeotroped in such a liquid, or extracted with such liquids toretain high porosity. Other pore preserving methods can also be usedsuch as adding a surfactant. One method of conveniently washing the gelis to dry it first, then wash it in an acid aqueous solution followed bya second drying.

[0050] The gel or precipitate then is dried. Any means of drying the gelknown in the art may be used, including spray drying, tray drying, flashdrying, rotary kiln drying, and the like. Preferably, the water in thegel is replaced with an organic liquid of lower surface tension beforebeing dried. If the gel has not been treated with an organic liquid torelieve surface tension, spray drying or flash drying is preferred.

[0051] Optionally, the gel is ground to a desirable particle size.Grinding through at least a 35 mesh screen is preferred. Mostpreferably, a 60 mesh screen is utilized. The oxide matrix compositionthus obtained can have a granular controlled particle size, and not thefine dusty consistency of the layered mineral.

[0052] The gel or precipitate must be calcined to produce the oxidematrix composition. The calcining can be completed in a dry inertatmosphere. Alternatively, the calcining can be completed in anoxidizing atmosphere, such as, oxygen or air, or a reducing atmosphere,such as, hydrogen or carbon monoxide. The calcining treatment can alsobe conducted in stages, as for example, the calcining treatment can beconducted first in an oxidizing atmosphere, then in a reducingatmosphere at a different temperature, or vice-versa. Preferably, thecalcining is completed in dry air or nitrogen at a temperature in arange of from about 150° C. to about 800° C., most preferably, from 200°C. to 500° C. Generally, this calcining is conducted for a time in therange of about 1 minute to about 100 hours, preferably for a time in therange of 3 to 20 hours. Methods of calcining are disclosed in U.S. Pat.Nos. 4,151,122; 4,177,162; 4,247,421; 4,248,735; 4,297,460; 4,397,769;and 4,460,756; the entire disclosures of which are hereby incorporatedby reference.

[0053] Generally, the oxide matrix composition comprises about 1 toabout 70% by weight residual mineral components. Preferably, the oxidematrix composition comprises about 2 to about 50% by weight residualmineral components, and most preferably, 10 to 30% by weight.

[0054] The oxide matrix composition provided by this invention has anamorphous structure. The decomposing or exfoliating step substantiallybreaks down the original layered structure of the mineral. This changecan be detected by the X-ray diffraction pattern taken of the oxidematrix composition. The sharp X-ray diffraction lines of the originalcrystalline layered mineral have been replaced by a simple, broadamorphous band, indicating loss of the original structure of the layeredmineral.

[0055] Another point of distinction of these novel oxide matrixcompositions is their high porosity. Whereas clay minerals usuallyexhibit very low pore volume, less than 0.3 mL/g, and even when pillaredusually less than 0.5 mL/g, the oxide matrix composition of thisinvention has pore volumes greater than about 0.75 mL/g, preferablygreater than about 1.0 mL/g, more preferably greater than about 1.3mL/g, and most preferably greater than 1.6 mL/g. Generally, the oxidematrix has a surface area greater than 200 m²/g, preferably greater than400 m²/g.

[0056] In accordance with another embodiment to produce the oxide matrixcomposition, a process is provided comprising: 1) substantiallydecomposing or exfoliating a layered mineral to produce residual mineralcomponents in the presence of an oxide precursor compound to produce aresidual mineral component/oxide precursor mixture; 2) subjecting saidresidual mineral/component mixture to such conditions to form a gel orprecipitate; and 3) drying and calcining said gel or precipitate at atemperature in a range of about 150° C. to about 800° C. to produce saidoxide matrix composition. Layered minerals, residual mineral components,oxide precursor compounds were previously discussed in this disclosure.In addition, methods of decomposing, gelling, drying, and calcining havealso been previously discussed in this disclosure.

[0057] In accordance with a second embodiment of this invention, theoxide matrix composition is provided. The oxide matrix compositioncomprises the residual mineral components and the oxide compound.Residual mineral components and the oxide compound were previouslydiscussed in this disclosure.

[0058] In accordance with a third embodiment of this invention, aprocess to produce a catalyst composition is provided. The processcomprises contacting an organometal compound, an organoaluminumcompound, and an oxide matrix composition to produce the catalystcomposition.

[0059] Organometal compounds used in this invention have the followinggeneral formula:

(X¹)(X²)(X³)(X⁴)M¹

[0060] In this formula, M¹ is selected from the group consisting oftitanium, zirconium, and hafnium. Currently, it is most preferred whenM¹ is zirconium.

[0061] In this formula, (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

[0062] Substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) can be selectedindependently from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic and cyclic groups, silyl groups, alkylhalide groups, halides, organometallic groups, phosphorus groups,nitrogen groups, silicon, phosphorus, boron, germanium, and hydrogen, aslong as these groups do not substantially, and adversely, affect thepolymerization activity of the catalyst composition.

[0063] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Substituted silyl groups include, but are not limited to, alkylsilylgroups where each alkyl group contains from 1 to about 12 carbon atoms,arylsilyl groups, and arylalkylsilyl groups. Suitable alkyl halidegroups have alkyl groups with 1 to about 12 carbon atoms. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0064] Suitable examples of such substituents are methyl, ethyl, propyl,butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl,chloro, bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

[0065] In this formula, (X³) and (X⁴) are independently selected fromthe group consisting of (hereafter “Group OMC-II”) halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic and substituted cyclic groups, amido groups,substituted amido groups, phosphido groups, substituted phosphidogroups, alkyloxide groups, substituted alkyloxide groups, aryloxidegroups, substituted aryloxide groups, organometallic groups, andsubstituted organometallic groups, as long as these groups do notsubstantially, and adversely, affect the polymerization activity of thecatalyst composition.

[0066] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Currently, it is preferred when (X³) and (X⁴) are selected from thegroup consisting of halides and hydrocarbyls, where such hydrocarbylshave from 1 to about 10 carbon atoms. However, it is most preferred when(X³) and (X⁴) are selected from the group consisting of fluoro, chloro,and methyl.

[0067] In this formula, (X²) can be selected from either Group OMC-I orGroup OMC-II.

[0068] At least one substituent on (X¹) or (X²) can be a bridging groupthat connects (X¹) and (X²), as long as the bridging group does notsubstantially, and adversely, affect the activity of the catalystcomposition. Suitable bridging groups include, but are not limited to,aliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, phosphorous groups, nitrogen groups, organometallicgroups, silicon, phosphorus, boron, and germanium.

[0069] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0070] Various processes are known to make these organometal compounds.See, for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305;5,401,817; 5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636;5,565,592; 5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284;5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203;5,654,454; 5,705,579; and 5,668,230; the entire disclosures of which arehereby incorporated by reference.

[0071] Specific examples of such organometal compounds are as follows:

[0072] bis(cyclopentadienyl)hafnium dichloride;

[0073] bis(cyclopentadienyl)zirconium dichloride;

[0074] 1,2-ethanediylbis(ρ⁵-1-indenyl)di-n-butoxyhafnium;

[0075] 1,2-ethanediylbis(75-1-indenyl)dimethylzirconium;

[0076] 3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafniumdichloride;

[0077] methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0078] bis(n-butylcyclopentadienyl)bis(di-t-butylamido) hafnium;

[0079] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0080] dimethylsilylbis(1-indenyl)zirconium dichloride;

[0081] octylphenylsilylbis(1-indenyl)hafnium dichloride;

[0082] dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0083] dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;

[0084] 1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;

[0085] indenyl diethoxy titanium(IV) chloride;

[0086] indenyl diethoxy titantium(IV) chloride;

[0087] (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;

[0088] bis(pentamethylcyclopentadienyl)zirconium dichloride;

[0089] bis(indenyl)zirconium dichloride;

[0090] methyloctylsilyl bis(9-fluorenyl)zirconium dichloride;

[0091]  and

[0092] bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate

[0093] Preferably, the organometal compound is selected from the groupconsisting of

[0094] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0095] bis(indenyl)zirconium dichloride;

[0096] dimethylsilylbis(1-indenyl)zirconium dichloride;

[0097]  and

[0098] methyloctylsilylbis(9-fluorenyl)zirconium dichloride

[0099] Organoaluminum compounds have the following general formula:

Al(X⁵)_(n)(X⁶)_(3−n)

[0100] In this formula, (X⁵) is a hydrocarbyl having from 1 to about 20carbon atoms. Currently, it is preferred when (X⁵) is an alkyl havingfrom 1 to about 10 carbon atoms. However, it is most preferred when (X⁵)is selected from the group consisting of methyl, ethyl, propyl, butyl,and isobutyl.

[0101] In this formula, (X⁶) is a halide, hydride, or alkoxide.Currently, it is preferred when (X⁶) is independently selected from thegroup consisting of fluoro and chloro. However, it is most preferredwhen (X⁶) is chloro.

[0102] In this formula, “n” is a number from 1 to 3 inclusive. However,it is preferred when “n” is 3.

[0103] Examples of such compounds are as follows:

[0104] trimethylaluminum;

[0105] triethylaluminum (TEA);

[0106] tripropylaluminum;

[0107] diethylaluminum ethoxide;

[0108] tributylaluminum;

[0109] diisobutylaluminum hydride;

[0110] triisobutylaluminum hydride;

[0111] triisobutylaluminum; and

[0112] diethylaluminum chloride.

[0113] Currently, TEA is preferred.

[0114] The process of producing the oxide matrix composition waspreviously discussed in this disclosure.

[0115] The catalyst compositions of this invention can be produced bycontacting the organometal compound, the organoaluminum compound, andthe oxide matrix composition, together. This contacting can occur in avariety of ways, such as, for example, blending. Furthermore, each ofthese compounds can be fed into a reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor.

[0116] Currently, one method is to first contact the organometalcompound and the oxide matrix composition together, for about 1 minuteto about 24 hours, preferably, 1 minute to 1 hour, at a temperature fromabout 10° C. to about 200° C., preferably 15° C. to 80° C., to form afirst mixture, and then contact this first mixture with anorganoaluminum compound to form the catalyst composition.

[0117] Another method is to precontact the organometal compound, theorganoaluminum compound, and the oxide matrix composition beforeinjection into a polymerization reactor for about 1 minute to about 24hours, preferably, 1 minute to 1 hour, at a temperature from about 10°C. to about 200° C., preferably 20° C. to 80° C.

[0118] A weight ratio of the organoaluminum compound to the oxide matrixcomposition in the catalyst composition ranges from about 5:1 to about1:1000, preferably, from about 3:1 to about 1:100, and most preferably,from 1:1 to 1:50.

[0119] A weight ratio of the oxide matrix composition to the organometalcompound in the catalyst composition ranges from about 10,000:1 to about1:1, preferably, from about 1000:1 to about 10:1, and most preferably,from 250:1 to 20:1. These ratios are based on the amount of thecomponents combined to give the catalyst composition.

[0120] After contacting, the catalyst composition comprises apost-contacted organometal compound, a post-contacted organoaluminumcompound, and a post-contacted oxide matrix composition. Preferably, thepost-contacted oxide matrix composition is the majority, by weight, ofthe catalyst composition. Often times, specific components of a catalystare not known, therefore, for this invention, the catalyst compositionis described as comprising post-contacted compounds.

[0121] A weight ratio of the post-contacted organoaluminum compound tothe post-contacted oxide matrix composition in the catalyst compositionranges from about 5:1 to about 1:1000, preferably, from about 3:1 toabout 1:100, and most preferably, from 1:1 to 1:50.

[0122] A weight ratio of the post-contacted oxide matrix composition tothe post-contacted organometal compound in the catalyst compositionranges from about 10,000:1 to about 1:1, preferably, from about 1000:1to about 10:1, and most preferably, from 250:1 to 20:1. These ratios arebased on the amount of the components combined to give the catalystcomposition.

[0123] The catalyst composition of this invention has an activitygreater than 1000 grams of polymer per gram of oxide matrix compositionper hour, preferably greater than 2000, and most preferably greater thanabout 3,000. This activity is measured under slurry polymerizationconditions, using isobutane as the diluent, and with a polymerizationtemperature of 90° C., and an ethylene pressure of 450 psig. The reactorshould have substantially no indication of any wall scale, coating orother forms of fouling.

[0124] One of the important aspects of this invention is that noaluminoxane needs to be used in order to form the catalyst composition.Aluminoxane is an expensive compound that greatly increases polymerproduction costs. This also means that no water is needed to help formsuch aluminoxanes. This is beneficial because water can sometimes kill apolymerization process. Additionally, it should be noted that nofluoro-organo borate compounds need to be used in order to form thecatalyst composition. The oxide matrix composition of this invention isinorganic when the oxide matrix is formed, heterogenous in a organicpolymerization medium, and can be can be easily and inexpensivelyproduced because of the substantial absence of any aluminoxane compoundsor fluoro-organo borate compounds. Layered minerals are not required inthe catalyst composition. It should be noted that organochromiumcompounds and MgCl₂ are not needed in order to form the catalystcomposition. Although aluminoxane, fluoro-organo borate compounds,layered minerals, organochromium compounds, and MgCl₂ are not needed inthe preferred embodiments, these compounds can be used in otherembodiments of this invention.

[0125] In another embodiment of this invention, a process comprisingcontacting at least one monomer and the catalyst composition to producea polymer is provided. The term “polymer” as used in this disclosureincludes homopolymers and copolymers. The catalyst composition can beused to polymerize at least one monomer to produce a homopolymer or acopolymer. Usually, homopolymers are comprised of monomer residues,having 2 to about 20 carbon atoms per molecule, preferably 2 to about 10carbon atoms per molecule. Currently, it is preferred when at least onemonomer is selected from the group consisting of ethylene, propylene,1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and mixtures thereof.

[0126] When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limited to, aliphatic 1-olefins havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefins and conjugated or nonconjugated diolefins such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefins and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally about0.01 to about 10 weight percent comonomer based on the total weight ofthe monomer and comonomer, preferably, about 0.01 to about 5, and mostpreferably, 0.1 to 4. Alternatively, an amount sufficient to give theabove described concentrations, by weight, in the copolymer produced canbe used.

[0127] Processes that can polymerize at least one monomer to produce apolymer are known in the art, such as, for example, slurrypolymerization, gas phase polymerization, and solution polymerization.It is preferred to perform a slurry polymerization in a loop reactionzone. Suitable diluents used in slurry polymerization are well known inthe art and include hydrocarbons which are liquid under reactionconditions. The term “diluent” as used in this disclosure does notnecessarily mean an inert material; it is possible that a diluent cancontribute to polymerization. Suitable hydrocarbons include, but are notlimited to, cyclohexane, isobutane, n-butane, propane, n-pentane,isopentane, neopentane, and n-hexane. Furthermore, it is most preferredto use isobutane as the diluent in a slurry polymerization. Examples ofsuch technology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

[0128] The catalyst compositions used in this process produce goodquality polymer particles without substantially fouling the reactor.When the catalyst composition is to be used in a loop reactor zone underslurry polymerization conditions, it is preferred when the particle sizeof the oxide matrix composition is in the range of about 10 to about1000 microns, preferably about 25 to about 500 microns, and mostpreferably, 50 to 200 microns, for best control during polymerization.

[0129] Hydrogen can be used with this invention in a polymerizationprocess to control polymer molecular weight.

[0130] After the polymers are produced, they can be formed into variousarticles, such as, for example, household containers and utensils, filmproducts, drums, fuel tanks, pipes, geomembranes, and liners. Variousprocesses can form these articles. Usually, additives and modifiers areadded to the polymer in order to provide desired effects. It is believedthat by using the invention described herein, articles can be producedat a lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

EXAMPLES

[0131] Testing Methods

[0132] A “Quantachrome Autosorb-6 Nitrogen Pore Size DistributionInstrument” was used to determined surface area and pore volume. Thisinstrument was acquired from the Quantachrome Corporation, Syosset, N.Y.Calcining Treatment: To calcine a specified material in these examples,about 10 grams were placed in a 1.75 inch quartz tube fitted with asintered quartz disk at the bottom. While the specified material wassupported on the disk, dry nitrogen was blown up through the disk at arate of about 1.6 to about 1.8 standard cubic feet per hour. An electricfurnace around the quartz tube was then turned on, and the temperaturewas raised at the rate of 400° C. per hour to the indicated temperature,which was 300° C. At that temperature, the specified material wasallowed to fluidize for three hours in the dry air to produce a calcinedmaterial. Afterward, the calcined material was collected and storedunder dry nitrogen, where it was protected from the atmosphere untilready for testing. It was never allowed to experience any exposure tothe atmosphere.

[0133] Polymerization Test Procedure: Polymerization runs were made in a2.2 liter steel reactor equipped with a marine stirrer running at 400revolutions per minute (rpm). The reactor was surrounded by a steeljacket containing boiling methanol with a connection to a steelcondenser. The boiling point of the methanol was controlled by varyingnitrogen pressure applied to the condenser and jacket, which permittedprecise temperature control to within half a degree Celsius, with thehelp of electronic control instruments.

[0134] Unless otherwise stated, a small amount (0.01 to 0.10 gramnormally) of a layered mineral, layered mineral mixture, or inventiveoxide matrix composition was first charged under nitrogen to a dryreactor. Next, 2.0 milliliters of a toluene solution containing 0.5percent by weight of bis(n-butylcyclopentadienyl) zirconium dichloridewere added to the reactor, followed by 0.6 liter of isobutane liquid.Then, 1.0 milliliter of a 1.0 molar solution of triethyl aluminum (TEA)was added, followed by another 0.6 liter of isobutane liquid. Then, thereactor was heated up to a specified temperature, typically 90° C., andfinally ethylene was added to the reactor to equal a fixed pressure,generally 450 psig unless otherwise stated, to produce a reactionmixture. The reaction mixture was allowed to stir for usually about onehour. As ethylene was consumed, more ethylene flowed in to maintain thepressure. The activity was noted by recording the flow of ethylene intothe reactor to maintain the set pressure.

[0135] After the allotted time, the ethylene flow was stopped, and thereactor slowly depressurized and opened to recover a granular polymer.In all cases, the reactor was clean with no indication of any wallscale, coating or other forms of fouling. The polymer was then removedand weighed. Activity was specified as grams of polymer produced pergram of the bentonite utilized or contained in a layered mineral mixtureor inventive oxide matrix composition per hour of reaction time.

CONTROL EXAMPLE 1

[0136] A fine Volclay bentonite was calcined in nitrogen for 3 hours toproduce a calcined bentonite. The calcined bentonite was found bynitrogen sorption to have a pore volume of about 0.17 milliliter pergram and a surface area of about 34 square meters per gram. The calcinedbentonite was tested for polymerization activity according to theprocedure described previously. It exhibited an activity of about 9590grams of polymer per gram of calcined bentonite per hour. The polymerwas very fine.

INVENTIVE EXAMPLE 2

[0137] 50 grams of the bentonite used in Example 2 were added to 1 literof water and allowed to stir for 2 hours at 70° C. to produce a firstmixture. In another beaker, 200 milliliters of tetraethoxysilane(Si(OEt)₄) containing 120 grams of silica were added to 500 millilitersof isopropanol along with 0.6 gram of sulfuric acid and 32.4 millilitersof water to produce a second mixture. There was not quite enough waterto hydrolyze the silica. The second mixture was stirred for 4 hours.Then, the first mixture was added to the second mixture to produce athird mixture. The third mixture became hot, indicating reaction of thetetraethoxysilane. The third mixture was allowed to stir for about twomore hours at which time it gelled spontaneously. Half of this gel wasthen dried in an oven under vacuum at 110° C. overnight. It then wasground through a 100 mesh screen and calcined at 300° C. to produce anoxide matrix composition. The oxide matrix composition was tested as anactivator for an organometal compound per the polymerization procedurediscussed previously. It yielded an activity of 11,687 grams of polymerper gram of bentonite used per hour, which is higher than ControlExample 1.

INVENTIVE EXAMPLE 3

[0138] The other half of the gel made in Example 2 (before drying,grinding, and calcining) was then aged by placing it in two liters ofn-propanol along with 30 milliliters of concentrated ammonium hydroxide(28% by weight NH3). This mixture was heated to 80° C. where it wasallowed to stir for 20 minutes. The gel was then filtered out and driedin the vacuum oven overnight at 110° C. to produce an aged gel. The agedgel then was calcined at 300° C. to produce an oxide matrix composition.The oxide matrix composition was not ground through a screen. It wastested for polymerization activity and found to yield 19,722 grams ofpolymer per gram of bentonite used per hour.

INVENTIVE EXAMPLE 4

[0139] A sample of the aged gel from example 3 before calcining wasground through a 100 mesh screen and calcined at 300° C. to produce anoxide matrix composition. The oxide matrix composition was found to havea pore volume of about 2.65 milliliter per gram and a surface area ofabout 468 square meters per gram. When tested for polymerizationactivity according to the procedures described previously, it yielded anactivity of 51,200 grams of polymer per gram of bentonite used per hour.

CONTROL EXAMPLE 5

[0140] Another, but unsuccessful, method of adding silica is illustratedby this example. 25 grams of Cabosil HS-5, an extremely fine silicaformed by flame hydrolysis, were added to 1 liter of water which washeated to 70° C. Then, 50 grams of bentonite were added to produce asilica/bentonite mixture. The silica/bentonite mixture was stirred fortwo hours, and then centrifuged to isolate the solids. The solids wereadded to two liters of n-propanol, which was heated to 60° C. andstirred for 20 minutes. The solids were removed again by centrifugationthen dried under vacuum at 110° C. After drying, the solids were groundthrough a 100 mesh screen and calcined at 300° C. in nitrogen to producea calcined silica/bentonite mixture. Upon testing for polymerizationactivity, it was found to yield 853 grams of polymer per gram ofbentonite used per hour.

CONTROL EXAMPLE 6

[0141] The following example demonstrates that the benefit shown inInventive Examples 2-4 is not simply a consequence of the aging step oralcohol wash step on the bentonite, nor can the bentonite be enhanced bysimply decomposing and reconstituting it. 50 grams of bentonite wereslurried in one liter of water to which 25 milliliters of concentratedammonium hydroxide were added to produce a first mixture. The firstmixture was heated to 80° C. and held at this temperature while stirringfor an hour. Then, it was centrifuged to remove solids. The solids thenwere slurried again in two liters of n-propanol to produce a secondmixture. The second mixture was heated to 60° C. and stirred for 20minutes. Then, the second mixture was centrifuged again to remove thesolids, and the solids were placed in a vacuum oven at 110° C. overnightto produce a decomposed, aged and reconstituted bentonite. Thedecomposed, aged, and reconstituted bentonite then was ground through a100 mesh sieve and calcined at 300° C. in nitrogen for three hours. Thismaterial was still found to exhibit an X-ray diffraction pattern,indicating a layered structure. Upon testing for polymerizationaccording to the procedure discussed previously, an activity of 2434grams of polymer per gram of decomposed, aged and reconstitutedbentonite per hour was observed.

[0142] INVENTIVE EXAMPLE 7

[0143] The following example demonstrates gellation of residualbentonite components in an alumina matrix. Ten grams of Catapal alumina(lot V2403A) were slurried in 200 milliliters of water. Then, onemilliliter of nitric acid was added, and the Catapal alumina dissolved(peptized) into a clear colloidal suspension to produce an acidicmixture. Then, 20 grams of bentonite were added to the acidic mixture.The acidic mixture was stirred and digested at 70° C. for two hours.Finally, 5 milliliters of concentrated ammonium hydroxide were added toneutralize the acidity to produce a gel. The gel was then vacuum driedat 110° C. overnight and ground through a 100 mesh screen. A sample wascalcined in nitrogen at 300° C. to produce an oxide matrix composition.The oxide matrix composition was tested for polymerization activity. Ityielded 6645 grams of polymer per gram of bentonite used per hour.

INVENTIVE EXAMPLE 8

[0144] 25 grams of Catapal alumina were added to one liter of water.Then, one milliliter of nitric acid was added to produce an acidicmixture, and the acidic mixture heated to 70° C. The alumina dissolved(peptized) into a clear colloidal suspension. Then, 50 grams ofbentonite were added to the acidic mixture to produce a second mixture.The second mixture was held for 2 hours at 70° C. Then, 5 milliliters ofconcentrated ammonium hydroxide were added to neutralize the secondmixture to produce a gel. Half of the gel then was freeze dried for fourdays. The freeze-dried gel was ground through a 35 mesh screen andcalcined in nitrogen at 300° C. to produce an oxide matrix composition.The oxide matrix composition was tested for polymerization activity. Ityielded 9797 grams of polymer per gram of bentonite used per hour.

INVENTIVE EXAMPLE 9

[0145] The other half of the gel from example 8 was then added to 2liters of n-propanol and stirred at 70° C. for half an hour to produce afirst mixture. Then, the first mixture was centrifuged to remove solids,and the solid were vacuum dried overnight at 110° C. The solids werethen ground through a 50 mesh screen and calcined in nitrogen at 300° C.to produce an oxide matrix composition. The new oxide matrix compositionwas tested for polymerization activity. It yielded 12,380 grams ofpolymer per gram of bentonite used per hour.

INVENTIVE EXAMPLE 10

[0146] 1.0 gram of bentonite was added to 100 milliliters of water andsonnicated for 45 minutes to produce a first mixture. Sonnification wasconducted using a Sonics Materials 500 watt Vibracell Sonicator, modelVC500, available from Sonics Materials, Danbury, Conn. It was set at 40%pulsed mode with a microtip limit of 7, using a Sonics Materials modelV14 horn. The first mixture became very viscous. Then, 146.36 grams ofaluminum nitrate nonahydrate were added to produce a second mixture. Thesecond mixture was stirred and heated to 70° C. for 15 minutes. 90milliliters of concentrated (28%) ammonia solution were added to thesecond mixture to produce a gel. The gel was diluted with 1 liter ofwater and further ammonia was added to adjust the pH to 10.5 to producea third mixture. The temperature was raised to 80° C., and the thirdmixture was stirred at this temperature and pH for one hour. The thirdmixture was then filtered, and the filtrate was washed in 1 liter ofisopropanol. After filtration, the filtrate was dried overnight at 110°C. under half an atmosphere of vacuum, then ground through a 35 meshscreen and calcined in nitrogen for three hours at 300° C. to produce anoxide matrix composition. The oxide matrix composition was tested in apolymerization run according to the procedure discussed previouslyexcept 550 psig of pressure was applied to the reactor. Only a smallactivity was observed.

INVENTIVE EXAMPLE 11

[0147] 5.12 grams of bentonite were slurried in 100 milliliters of waterto produce a first mixture. The first mixture was sonnicated for 65minutes. The first mixture became very viscous. Then, 146.35 grams ofaluminum nitrate nonahydrate were added together with 800 milliliters ofwater to the first mixture to produce a second mixture. The secondmixture was stirred and heated to 70° C. for 15 minutes. 90 millilitersof concentrated (28%) ammonia solution were added to the second mixtureto produce a gel. The gel was diluted with 1 liter of water and furtherammonia added to adjust the pH to 10.0 to produce a third mixture. Thetemperature was raised to 80° C., and the third mixture was stirred atthat temperature and pH for one hour. The third mixture was thenfiltered, and the filtrate was washed in 4 liters of n-propanol at 60°C. After filtration, the gel was dried overnight at 110° C. under halfan atmosphere of vacuum to produce a dried powder. The dry powder wasground through a 35 mesh screen and calcined in nitrogen for three hoursat 300° C. to produce an oxide matrix composition. The oxide matrixcomposition was tested in a polymerization run according to theprocedure discussed previously except 550 psig of pressure was appliedto the reactor. Only a small activity was observed.

[0148] INVENTIVE EXAMPLES 12 & 13

[0149] 1.0 gram of bentonite was slurried in 100 milliliters of water towhich 3 milliliters of concentrated nitric acid were added to produce afirst mixture. The first mixture was sonnicated for 65 minutes andbecame very viscous. Then, 19.43 grams of aluminum nitrate nonahydratewere added to produce a second mixture. The second mixture was stirredand heated to 60° C. for 20 minutes. 35 milliliters of concentrated(28%) ammonia solution were added to the second mixture to causegellation. The gel was diluted with 1 liter of water and further ammoniawas added to adjust the pH to 10.3 to produce a third mixture. Thetemperature was raised to 60° C., and the third mixture stirred at thattemperature and pH for one hour. It was then diluted with one liter ofwater and stirred at 60° C. After filtration, the third mixture waswashed twice in 1 liter of n-propanol and finally dried overnight at110° C. under half an atmosphere of vacuum to produce a dry powder. Thedry powder was ground through a 35 mesh screen and calcined in nitrogenfor three hours at 300° C. to produce an oxide matrix composition. Itthen was tested for polymerization activity as described previouslyexcept that 550 psig pressure was applied to the reactor (Example 12).The new oxide matrix composition was also tested a second time in thereactor at the normal 450 psig pressure (Example 13). X-ray diffractionindicated only the broad peaks, which illustrated that the bentonite hadbeen decomposed to its residual components forming a new structure.

INVENTIVE EXAMPLE 14

[0150] 2.66 grams of bentonite were added to 100 milliliters of waterand sonnicated for 1 hour to produce a first mixture. Then, 111 grams ofsodium silicate solution (27% silica) were added to the first mixturealong with 100 milliliters of water to produce a second mixture. Thesecond mixture was heated to boiling for about 30 minutes. It wasallowed to cool and sit overnight. Then, 20 milliliters of concentratednitric acid were added to the second mixture to neutralize the sodiumsilicate and produced a gel. The gel was then washed four times in 4liters of water containing 10 milliliters of galatial acetic acid tocause the wash pH to be slightly acid. The gel was then given a finalwash in 4 liters of n-propanol and dried overnight. The gel was groundthrough a 35 mesh screen and calcined at 300° C. in nitrogen for threehours to produce an oxide matrix composition. The oxide matrixcomposition was tested in a polymerization run according to theprocedure discussed previously except that 550 psig pressure was appliedto the reactor. An activity of 20,213 grams of polymer per gram ofbentonite used was observed.

INVENTIVE EXAMPLES 15 & 16

[0151] 1.0 gram of bentonite was sonnicated for 1 hour in 100milliliters of water containing 2.0 milliliters of concentrated nitricacid to produce a first mixture. The first mixture became very viscous.The first mixture was added to a solution containing 300 milliliters ofn-propanol and 33 milliliters of silicon tetraethoxide to produce asecond mixture. The second mixture was stirred for one hour, and then,10 milliliters of concentrated ammonia solution (28%) were added toneutralize the nitric acid and thus cause gellation. The gel then wasaged when 100 milliliters n-propanol were added, and it was heated to80° C. and stirred for one hour. The gel was washed in 1 liter ofn-propanol and dried overnight. The gel then was ground through a 35mesh screen and calcined in nitrogen at 300° C. for three hours toproduce an oxide matrix composition. The oxide matrix composition wasfound to have a pore volume of about 2.46 milliliter per gram and asurface area of 635 square meters per gram. The oxide matrix compositionwas tested for polymerization activity as described previously exceptthat 550 psig pressure was applied to the reactor (Example 15). InExample 15, an activity of 42,172 grams of polymer per gram of bentoniteused per hour was observed. The oxide matrix composition also was testeda second time under the normal 450 psig pressure (Example 16). InExample 16, an activity of 18,604 grams of polymer per gram of bentoniteused per hour was observed. X-ray diffraction indicated only broad peakswhich indicates that the bentonite had been decomposed to its residualcomponents. The X-ray diffraction pattern of the oxide matrixcomposition is shown in FIG. 1 along with the original bentonite controlof Example 1.

INVENTIVE EXAMPLE 17

[0152] 1.0 gram of bentonite was sonnicated for 1 hour in 100milliliters of water containing 10 milliliters of ammonia solution (28%by weight) to produce a first mixture. The first mixture then was addedto 300 milliliters of n-propanol containing 34 milliliters of silicontetraethoxide to produce a second mixture. The second mixture was boiledfor 30 minutes during which time a gel formed. An additional 50milliliters of n-propanol then were added to the gel to form a thirdmixture. The gel was allowed to settle out from the third mixture. Thesupernatant liquid of the third mixture was poured off, and 500milliliters of n-propanol were added again. This process was repeatedfive times before the gel was allowed finally to dry overnight. The gelwas ground through a 35 mesh screen and calcined in nitrogen at 300° C.for three hours to produce an oxide matrix composition. The oxide matrixcomposition was found to have a pore volume of about 2.36 millilitersper gram and a surface area of about 388 square meters per gram. Theoxide matrix composition then was tested for polymerization activity asdescribed previously except that 550 psig pressure was applied to thereactor. An activity of 27,602 grams of polymer per gram of bentoniteused per hour was observed. TABLE 1 Summary of Examples Bentonite WtCharged To g Polymer Reaction Activity Example Test Material Conc.(a)Aging Last Wash Drying Reactor Produced Time, min g/g/h  1-ControlBentonite 1.00 no None none 0.0078 74.8 60 9590  2-Inventive OxideMatrix (silica gel from Si(OEt)₄) 0.25 no Alcohol oven 0.0243 71 6011687  3-Inventive Oxide Matrix (silica gel from Si(OEt)₄) 0.25 yesAlcohol oven 0.0144 71 60 19722  4-Inventive Oxide Matrix (silica gelfrom Si(OEt)₄) 0.25 yes Alcohol oven 0.0025 32 60 51200  5-ControlCabosil Silica/Bentonite Mixture 0.67 no Alcohol oven 0.007 2 30 853 6-Control Decomposed, Aged, Reconstituted 1.00 yes Alcohol oven 0.0843171 50 2434 Bentonite  7-Inventive Oxide Matrix (Catapal Alumina) 0.67no Water oven 0.0283 126 60 6645  8-Inventive Oxide Matrix (CatapalAlumina) 0.67 no water freeze dry 0.0227 149 60 9797  9-Inventive OxideMatrix (Catapal Alumina) 0.67 yes alcohol oven 0.0217 180 60 1238010-Inventive Oxide Matrix (Alumina from Al(NO₃)₃) 0.0476 yes alcoholoven 0.7416 3 60 85 11-Inventive Oxide Matrix (Alumina from Al(NO₃)₃)0.204 yes alcohol oven 0.5020 0 60 0 12-Inventive Oxide Matrix (Aluminafrom Al(NO₃)₃) 0.275 yes alcohol oven 0.2240 179 30 5812 13-InventiveOxide Matrix (Alumina from Al(NO₃)₃) 0.275 yes alcohol oven 0.1327 21260 5781 14-Inventive Oxide Matrix (silica from water glass) 0.0814 yesalcohol oven 0.0936 77 30 20213 15-Inventive Oxide Matrix (silica gelfrom Si(OEt)₄) 0.095 yes alcohol oven 0.1238 248 30 42173 16-InventiveOxide Matrix (silica gel from Si(OEt)₄) 0.095 yes alcohol oven 0.1572213 46 18604 17-Inventive Oxide Matrix (silica gel from Si(OEt)₄) 0.0925yes alcohol Oven 0.0376 96 60 27602

[0153] While this invention has been described in detail for the purposeof illustration, it is not intended to be limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A process to produce an oxide matrixcomposition, said process comprising: 1) substantially decomposing orexfoliating at least one layered mineral to produce residual mineralcomponents; wherein said layered mineral is a clay, clay mineral, or ionexchanging compound having a layered crystal structure; 2) contactingsaid residual mineral components and at least one oxide precursorcompound to produce a first mixture; wherein said oxide precursorcompound is selected from the group consisting of a silica source,alumina source, phosphate source; or combinations thereof; 3) subjectingsaid first mixture to such conditions to form a gel or precipitate; and4) drying said gel or precipitate and then calcining said gel orprecipitate at a temperature in a range of about 150° C. to about 800°C. to produce said oxide matrix composition.
 2. A process according toclaim 1 wherein said decomposing or exfoliating is accomplished bycontacting said layered mineral with a digestion agent selected from thegroup consisting of an aqueous solvent or other protic solvent followedby a) high shear mixing, b) high energy sonnification, or c) grinding ormilling to produce a colloidal suspension of said residual mineralcomponents.
 3. A process according to claim 1 wherein said gel is formedby adjusting the pH of said first mixture to a pH in a range of about 4to about
 9. 4. A process according to claim 1 further comprising agingsaid gel for about 5 minutes to about 10 hours at a temperature in arange of about 60 to 100° C. prior to drying and calcining to produce anaged gel or precipitate.
 5. A process according to claim 4 furthercomprising washing said aged gel prior to drying and calcining to removeundesirable ions.
 6. A process according to claim 5 further comprisinggrinding said gel to a desirable particle size prior to calcining.
 7. Aprocess to produce an oxide matrix composition, said processcomprising: 1) substantially decomposing or exfoliating a layeredmineral to produce residual mineral components in the presence of anoxide precursor compound to produce a residual mineral component/oxideprecursor mixture; wherein said layered mineral is a clay, clay mineral,or ion exchanging compound having a layered crystal structure; whereinsaid oxide precursor compound is selected from the group consisting of asilica source, alumina source, a phosphate source; or combinationsthereof. 2) subjecting said residual mineral/component mixture to suchconditions to form a gel or precipitate; and 3) drying said gel orprecipitate and then calcining said gel or precipitate at a temperaturein a range of about 150° C. to about 800° C. to produce said oxidematrix composition.
 8. A process according to claim 7 wherein saiddecomposing or exfoliating is accomplished by contacting said layeredmineral with a digestion agent selected from the group consisting of anaqueous solvent or other protic solvent followed by a) high shearmixing, b) high energy sonnification, or c) grinding or milling toproduce a colloidal suspension of said residual mineral components.
 9. Aprocess according to claim 8 wherein said gel is formed by adjusting thepH of said residual mineral component/oxide precursor mixture to a pH ina range of about 4 to about
 9. 10. A process according to claim 7further comprising aging said gel for about 5 minutes to about 10 hoursat a temperature in a range of about 60 to 100° C. prior to drying andcalcining to produce an aged gel or aged precipitate.
 11. A processaccording to claim 10 further comprising washing said aged gel orprecipitate prior to drying and calcining to remove undesirable ions.12. A process according to claim 11 further comprising grinding said gelor precipitate to a desirable particle size prior to calcining.
 13. Anoxide matrix composition produced by claim
 1. 14. An oxide matrixcomposition produced by claim
 7. 15. An oxide matrix compositioncomprising residual mineral components and at least one oxide precursorcompound; wherein said residual mineral components are produced bysubstantially decomposing or exfoliating a layered mineral to produceresidual mineral components; wherein said layered mineral is a clay,clay mineral, or ion exchanging compound having a layered crystalstructure; and wherein said oxide precursor compound is selected fromthe group consisting of a silica source, alumina source, a phosphatesource, Or combinations thereof.
 16. An oxide matrix composition madeaccording to claim 1 having an amorphous X-ray diffraction pattern. 17.An oxide matrix composition made according to claim 7 having anamorphous X-ray diffraction pattern.
 18. An oxide matrix compositionmade according to claim 1 having a pore volume greater than 1.0 mL/g.19. An oxide matrix composition made according to claim 7 having a porevolume greater than 1.0 mL/g.
 20. A process to produce a catalystcomposition, said process comprising contacting an organometal compound,an organoaluminum compound, and an oxide matrix composition to producesaid catalyst composition, wherein said organometal compound has thefollowing general formula: (X¹)(X²)(X³)(X⁴)M¹ wherein M¹ is selectedfrom the group consisting of titanium, zirconium, and hafnium; wherein(X¹) is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls; wherein substituentson said substituted cyclopentadienyls, substituted indenyls, andsubstituted fluorenyls of (X¹) are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic and cyclicgroups, silyl groups, alkyl halide groups, halides, organometallicgroups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron,germanium, and hydrogen; wherein at least one substituent on (X¹) can bea bridging group which connects (X¹) and (X²); wherein (X³) and (X⁴) areindependently selected from the group consisting of halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups; wherein (X²) is selected from thegroup consisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, substituted fluorenyls,halides, aliphatic groups, substituted aliphatic groups, cyclic groups,substituted cyclic groups, combinations of aliphatic groups and cyclicgroups, combinations of substituted aliphatic groups and cyclic groups,combinations of aliphatic groups and substituted cyclic groups,combinations of substituted aliphatic groups and substituted cyclicgroups, amido groups, substituted amido groups, phosphido groups,substituted phosphido groups, alkyloxide groups, substituted alkyloxidegroups, aryloxide groups, substituted aryloxide groups, organometallicgroups, and substituted organometallic groups; wherein substituents on(X²) are selected from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic groups and cyclic groups, silylgroups, alkyl halide groups, halides, organometallic groups, phosphorusgroups, nitrogen groups, silicon, phosphorus, boron, germanium, andhydrogen; wherein at least one substituent on (X²) can be a bridginggroup which connects (X¹) and (X²); wherein said organoaluminum compoundhas the following general formula: Al(X⁵)_(n)(X⁶)_(3−n) wherein (X⁵) isa hydrocarbyl having from 1 to about 20 carbon atoms; wherein (X⁶) is ahalide, hydride, or alkoxide; and wherein “n” is a number from 1 to 3inclusive; and wherein said oxide matrix composition is produced by theprocess of claim
 1. 21. A process to produce a catalyst composition,said process comprising contacting bis(n-butylcyclopentadienyl)zirconiumdichloride, triethylaluminum, and an oxide matrix.
 22. A catalystcomposition produced by the process of claim
 20. 23. A catalystcomposition produced by the process of claim
 21. 24. A catalystcomposition according to claim 22 wherein said catalyst composition hasan activity greater than 1000 under slurry polymerization conditions,using isobutane as a diluent, with a polymerization temperature of 90°C., and an ethylene pressure of 450 psig.
 25. A process according toclaim 24 wherein said catalyst composition has an activity greater than2000 under slurry polymerization conditions, using isobutane as adiluent, with a polymerization temperature of 90° C., and an ethylenepressure of 450 psig.
 26. A catalyst composition according to claim 22wherein a weight ratio of said organoaluminum compound to said oxidematrix composition in said catalyst composition ranges from about 3:1 toabout 1:100.
 27. A catalyst composition according to claim 26 whereinsaid weight ratio of said organoaluminum compound to said oxide matrixcomposition in said catalyst composition ranges from 1:1 to 1:50.
 28. Acatalyst composition according to claim 22 wherein a weight ratio ofsaid oxide matrix composition to said organometal compound in saidcatalyst composition ranges from about 1000:1 to about 10:1.
 29. Acatalyst composition according to claim 28 wherein said weight ratio ofsaid oxide matrix composition to said organometal compound in saidcatalyst composition ranges from 250:1 to 20:1.
 30. A polymerizationprocess comprising contacting at least one monomer and said catalystcomposition of claim 22 under polymerization conditions to produce apolymer.
 31. A process according to claim 30 wherein said polymerizationconditions comprise slurry polymerization conditions.
 32. A processaccording to claim 31 wherein said contacting is conducted in a loopreaction zone.
 33. A process according to claim 32 wherein saidcontacting is conducted in the presence of a diluent that comprises, inmajor part, isobutane.
 34. A process according to claim 33 wherein atleast one monomer is ethylene.
 35. A process according to claim 34wherein at least one monomer comprises ethylene and an aliphatic1-olefin having 3 to 20 carbon atoms per molecule.
 36. A polymerproduced in accordance with the process of claim
 30. 37. An article thatcomprises said polymer produced according to claim 36.